Recovery of oxygenated compounds and hydrocarbons from mixtures thereof



Dec. l2, 1950 R. F. MARscHNER RECOVERY 0F OXYGENATED COMPOUNDS AND mRocARBoNs mou mxTuREs mEREoF Filed oct. so, 1945 [rn/enfer?- Rober F.' Marsa/mer 5j @Magmey Patented Dec. 12, 1950 2,533,675 RECOVERY OF OXYGENATED COMPOUNDS AND HYDROCARBONS FROM MIXTURES THEREOF Robert F. Marschner, Homewood, Ill., assignor to Standard Oil Company, Chicago, Ill., a corporation of Indiana Application October 30, 194'5, Serial No. 625,519

4 Claims. (.Cl. 26o-450) A l This invention ,relates to the recovery of generically different types of components from a gasiform stream of reaction products. More particularly the invention relates to an improved combination oi.' synthesizing hydrocarbons and 5 their oxygenated compounds from mixtures ing the components oi such synthesis products.

In the conversion of hydrogen and carbon monoxide with a synthesis catalyst to produce hydrocarbons having more than one carbon atom to the molecule, a mixture of generically different types oi components is produced, including organic oxygenated compounds and hydrocarbons. A substantial proportion of the synthesis product comprises organic oxygenated compounds and these appear in the produced hydrocarbon liquids, in the .water of reaction, and in the gas streams beyond the liquid product recovery.

It is an object of this invention to eilect recovery of the reaction products in a plurality of integrated steps. It is a further object of this invention to recover separately generically diii'erent types of components from a reaction product stream including water. Another object of the invention is to provide a system wherein fractions oi the generically different components are utilized in the recovery of additional quantities of dissimilar components from the hydrocarbon synthesis product. Still another object is to provide a method and means for eilecting optimum recovery of synthesis -products in an eiiicient and expeditious manner. These and additional objects will become apparent as the description proceeds.

In its broader aspects the objects of this invention are attained by cooling an eflluent stream at reaction pressure to a temperature within the range oi between about 50 and 250 F. and forming two liquid phases in a separator which are withdrawn separately, while the uncondensedy wherein a partial condensation of the product water is eiiected. A substantial proportion oi the Arecoverable organic oxygenated compounds is -iound in this condensed water which is recovered 6o Alternatively organic oxygenated compounds in Ahydrogen and carbon monoxide and of recoveg/ of 'organic oxygenated compounds. These compounds have been identied as including among others: formaldehyde, acetaldehyde, acetone. methyl ethyl ketone and methyl, ethyl, n-,propyl and n-butyl alcohols.

The uncondensed stream of rich gas from the product separator is scrubbed under pressure with liquid wash water which is then added to the liquid product water phase. The combined water phases are distilled to give a light organic distillate, an aqueous distillate including organic oxygenated compounds and a residue or acid liquor winch is withdrawn from the system. The washed rich gas is passed into a sorption zone wherein a dry gas fraction and a hydrocarbon fraction plus residual organic oxygenated compounds are separated. The sorption may be effected by means ot a solid adsorbent or by means of a liquid absorbent. The lean gas is removed from the sorption zone and can be recycled to the reforming or to the synthesis step with or without separation of carbon dioxide as required.

The sorbed hydrocarbons and organic oxygenated compounds and the hydrocarbons recovered from the primary separator can be supplied to a liquid scrubber or extractor where organic oxygenated compounds are removed from the hydrocarbon constituents and the hydrocarbons are removed from the aqueous product fraction. The enriched aqueous oxygenated compound'traction can be withdrawn from the scrubber or extractor and supplied as the wash liquid in the gas scrubber. In the gas scrubbing operation the bulk of organic oxygenated compounds are removed from the rich gas and the light hydrocarbons are stripped from the aqueous liquor. A hydrocarbon fraction substantially free of oxygenated compounds is withdrawn from the extractor to be fractionated and/or treated as desired. The recovered organic oxygenated com- .'pounds from the aqueous product fraction still can be separated into relatively pure streams by fractionation or the like.

In the sorption zone the eilective agent may be charcoal, silica gel, alumina or other adsorptive material. The hydrocarbons adsorbed on these active agents can be removed by stripping or the like. Alternatively the washed, richgas supplied to the sorption zone can be freed 'of liquid hydrocarbons and organic oxygenated compounds by absorption with a suitable liquid, such for exfrom a primary separator, the water layery corn-gY Y prising between about 2 and about 20% or more ample as a liquid hydrocarbon product fraction.

the water phase can be recovered by distilling :the aqueous mixture of oxygenated compounds and water in the presence of added Cs--Cv hydrocarbons boiling between about 90 and 210 F. A mixture corresponding to the ternary azeotro-pe of hydrocarbons,l oxygenated compounds, and a minor proportion of water can be continuously removed as a constant-boiling mixture. The constituents of the azeotrope can then be recovered separately in substantially pure form.

The invention will be more clearly understood from the following detailed description of a specific example read in conjunction with the accompanying diagrammatic iiow sheet which forms a part of this specification and which represents a schematic ilow diagram of my improved system.

Natural gas from wells, which normally comprises essentially methane as its hydrocarbon constituent, is the preferred ultimate source of raw material for the process, although it should be understood that many features of the process are also applicable to feed gases derived directly or indirectly from other sources. such as coal. shale and carbonaceous material in general. It is also contemplated that suitable raw material either as hydrocarbon gases or as mixtures of hydrogen or carbon monoxide can be recovered from petroleum refining operations. The feed gases can, for example, be derived by the controlled regeneration of solid conversion catalyst having carbonaceous deposits thereon to produce carbon monoxide mixtures directly. In some instances, it will be necessary to alter the ratio of hydrogen to carbon monoxide, however, to obtain the optimum feed gas ratios.

The hydrocarbon gas is reformed to produce the desired hydrogen to carbon monoxide ratio which can be in the approximate ratio of between 0.5 to 1 and 3 to 1. A feed gas mixture containing hydrogen and carbon monoxide' in these ratios can be prepared by reforming natural gas either with oxygen, water, carbon dioxide, or admixtures of any of these at a temperature of between about 1400 and about 1800 F. and a pressure of between about atmospheric and 400 pounds per square inch thermally or over known types of catalyst. A preferred catalyst is a group VIII metal or metal oxides. It can be supported on a carrier, such as Super Filtrol, Celite, silica gel, clay, alumina, or the like. Nickel on alumina is particularly useful at a temperature of about 1600 F. The hydrogen-carbon monoxide mixture is withdrawn from the reformer and introduced into the hydrocarbon synthesis reactor at a pressure substantially that of the conversion step which may be about 300 pounds gauge.

The feed gas together with recycle gases are supplied to a cynthesis reactor. 'Ihe reactor may be of the fixed, moving bed or fiuidized type, and should be provided with means for abstracting the heat of synthesis to maintain the synthesis temperature within a relatively narrow range. Fixed beds of the tubular, chamber, annulus, shelf or divided types can be used, but a reactor of the so-called iluidized catalyst type, i. e., one designed to maintain'iinely divided catalyst in dense suspended turbulent or liquid-like phase, is particularly useful for this purpose. I'he reaction can be conducted under a pressure within the approximate range of between about 50 and about 500 pounds or more per square inch and at a temperature within the approximate range of between about 350 and 850 F., for example, 610 F.

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and 5000, or more, volumes of gas per volume of catalyst within the reactor are contemplated. 'I'he gas volumes are measured'at 60F. and under atmospheric pressure and the catalyst volume is based upon the iluidized catalyst within the synthesis reactor. The desired temperature level can be maintained by cooling tubes, by abstracting heat from the catalyst outside the reactor and recycling the cooled catalyst, by injecting cooling fluid directly into the reaction space, by recycling gaseous reaction products or liquid reaction products, etc.

A suitable catalyst for the synthesis is preferably one or more group VIII metals or metal oxides. for example, nickel, iron, or cobalt. A particularly useful catalyst-is an iron-type catalyst similar to that used irr ammonia synthesis.

Catalysts outside group VDI can also be used. In some instances it is desirable to include promoters comprising metals or metal compounds such as the oxides of aluminum, cerium, magnesium, manganese, potassium, thorium, titanium, uranium, zinc, zirconium, and the like. If desired, the catalyst can be supported on a suitable carrier such as clay, silica gel, alumina, Super Filtrol, Celite, etc.

For use in a uidized system the catalyst particles are of the order of 2 to 200 microns or larger, preferably 20 to 100 microns in particle size. With vertical gasiform uid velocities of the order of about 0.5 to 5, preferably between about l and 4, for example, about 2 feet per second, a liquid-like dense phase of catalyst is obtained in which the bulk density is between about 30 and about 90 percent, preferably between about 40 and 80, e. g. about 60 percent of the density of the settled catalyst material within the reactor.

The absolute density of the catalyst particles employed decreases with the on-stream time and it is contemplated that the vertical gasiform velocities can be diminished and/ or the quantity of catalyst reduced to maintain the desired fiuidized bulk density of catalyst within the reactor. In any event the vertical velocity of the gasiform fluids is regulated so as to produce a turbulent suspension of catalyst material within the reactor.

The catalyst material is continuously settled from the reaction products within the reactor, any residual catalyst in 'the gaseous product being removable by water scrubbing, cyclone separators, or the like. However, since the reaction system is not a feature of the present invention, it has not been illustrated and further details have not been described. Y

The reaction product stream in line I0 is cooled in partial condenser Il and the cooled mixture introduced into primary separator I2l together with rich scrubber' water in line I9.'

which includes methyl alcohol and other oxy-` genated compounds. The oxygenated compounds y ,ssaers will conprisesbetween about about l0 mol percent of the aqueous phase introduced into the still It. The still Il may be operated at a pressure between-about atmospheric and 100 pounds per square inch, and a pressure reducing 'valve' (not shown) can be provided on line Il. The rich water can be introduced in to the still Il at a temperature of about 150 1".. and a suitable heat source 2l can be provided near the base of the still Il. Alternatively, opensteam can be introduced into still Il to.sup'piy heat thereto. The overhead from' the still It can be withdrawn by line 21 for recoveryof light organic products. An acid liquor traction can b'e withdrawn from the still Il via line 22. the lean water withdrawn 4representing the net production of reaction water. When it isdesired to employ azeotropic distillation. a Cs-lC-I fraction can be heated in Il and introduced into the still Il via line 2.2. This hydrocarbon fraction can suitably 'be a'product fraction recovered from the hydrocarbon product in i'ractionator I via lin'e I2. In that event. the lconstant boiling mixture can be withdrawn overhead from the still I 0 via line 21..

An aqueous -liquor including dissolved oxygenated compounds is withdrawn from an Intermecurrently contacted with hydrocarbons and oxygenated compounds supplied by lines I 2 and 2l.

In the extractor I4 oxygenated compounds are removed from the hydrocarbons by the aqueous phase and hydrocarbons substantially free of purpose and the hydrocarbons canbe released from such adsorbents by stripping, for example with steam. When steam is used, the adsorbent em-uent can be collected to produce two liquid drocarbon and the condensed water. When a liquid absorbent is employed in the recovery of hydrocarbons from the rich gas within the sorptlon zone 2 I, a suitable absorbent medium is a gas oil fraction recovered from the hydrocarbon product in fractionator Il vla line 33 andthe hydrocarbons recovered therefrom by, distillation. The residual gases from the sorption stellare rich in hydrogen but may contain low molecular weight hydrocarbons and carbon dioxide. If desired these gases can be passed thru a second sorption step for the recovery oi' residual hydrocarbons before being vented from the system via line 2l. Alternatively. all or a portionof `the gases can be recycled to the hydrocarbon reformer or to the synthesis reactor. It is also contemplated that the CO: can be removed from the tail 'gases and supplied to the reformer and any unconverted feed recycled to the synthesis reactor.

The rich liquids from the sorber 2I are withdrawn via line 21 and commingled with the hydncarbon product fractionwithdrawn by line. Il

light oxygenated compounds are recovered via line 30. f

The hydrocarbons withdrawn from the liquid scrubber I4 via line 3l and passed through heater or exchanger 2l are substantially free of light organic oxygenated compounds. This vapor iraction can be introduced into the fractionator 3| gas is by absorption. The rich absorber liquid -`can be withdrawn from sorption zone 2I and fractionated in a separate still (not shown) or re- "cy'cled to the fractionator system 2i directly or via the scrubber I4.

The rich'gas from primary separator I2 is introduced vialine 23 at a low point into the gas scrubber Il. Within scrubber Il water soluble synthesis products are recovered by contacting with an enriched aqueous liquor introduced via line 24 from the liquid scrubber I4. The further enriched liquor is withdrawn from the scrubber I'I .via line Il and processed as herein described.

The washed rich gas removed from the gas scrubber I1 via line 25 is introduced into the sorption zone 2i. Within sorption zone 2I the hydrocarbon constituents are recovered from the rich gas and a dry gas is separated via line 2i. The recovery of hydrocarbons within the sorption zone 2I can be eiiected by means of a solid adsorbent or a liquid absorbent.

The solid adsorbents can be selected from a number of well known materials useful lor this from the primary separator I2. The commingled stream is then introduced into liquid scrubber I4 wherein the hydrocarbons are contacted in the liquid phase with aqueous liquor introduced by line 28 from the still I6., f

The liquid product from the liquid scrubber i4 can be fractionated in .3| to produce the desired cuts such as Diesel fuel, wax, gasoline, etc. These product fractions can be recovered via lines 22,

13, 24 and 35. =In the embodiment illustrated, a

Cs-C-r cut suitable for use in the ,azeotropic distillation of the oxygenated compounds from the water phases can be recovered by line 32,heated in Il and supplied to still I6. An absorber oil traction can be recovered by line 33 and supplied to sorber 2|. The rich absorber oil can be returned to the fractionator 3| via the liquid scrubber I4. Alternatively, a. separate stripper system can be provided for the rich absorber oil. bypassing the liquid scrubber I4. d

If desired, the hydrocarbon product fractions in lines I3 and 21 from separator I2 and'sorber 2l, which includes oil-soluble oxygenated compounds. can be catalytically finished. For exampie, the product fraction can be heated to a teinperature of between about 750 and 800 F. and contacted with a cracking catalyst to convert the oxygenated compounds to oleilns. Suchen operation does not etfect any reforming or cracking and the octane number improvement results from the conversion of the oxygenated compounds to oleiins. However, this catalytic iin- .ishing can be conducted at a higher temperature of the order of between 925 F. and about 975 F. which not only converts the oxygenated compounds. to hydrocarbons but also effects reforming of the gasoline hydrocarbons and cracking of the heavier hydrocarbon product to produce a material of improved anti-knock and of lower molecular weight.

It is also contemplated that instead of employing a single primary separator, I may provide a means for cooling the reaction product in stages waxes. The remainder of the gasiform product can then be further cooled to a temperature of about to 100 F. below the boiling point of the water at the partial pressure oi' water existing in the product stream. A liquid water fraction can then be recovered which is substantially free of any condensable oxygenated compounds. Further cooling of the gasiform product stream will permit the separation of a concentrated solution or oxygenated compounds as the water phase. When fractional condensation is employed, the pure water fraction can be used in the two-phase absorber Il, the oxygenated compounds being subsequently removed and the water discarded.

Although fractionation has been described as the means of recovering the oxygenated com-Y pounds present in the aqueous phase from separator I2 and gas scrubber I1, it is to be understood that other means can be employed. The stream of oxygenated compounds and water in lines I5 and I9 can be treated by any method to recover the separate components as desired. Other means may be used for recovery of the oxygenated compounds in the aqueous phase such as extraction with a suitable solvent or conversion of the alcohols present to the more volatile aldehydes and ketones and subsequent recovery of all aldehydes and ketones present by stripping or by the addition of sodium bisulte to precipitate the compounds formed with regeneration of the aldehydes and ketones by the addition of acid.

From the above description it will be apparent that my invention provides a novel method and means for recovery of products from a reaction stream such as from a hydrocarbon synthesis and an integrated system for attaining the objects of my invention. However, to simplify the description, valves, pumps and similar control means have not always been included. It is also contemplated that the exothermic heat of the reaction can be utilized in supplying heat to the stripping and fractionation step.

It is to be understood that although my invention has been described with reference to an i1- lustrative example, the invention is not restricted thereto and that modifications by those skilled in the art are contemplated without departing from the spirit of the invention defined by the appended claims.

What I claim is:

1. In a process for separately recovering generically different types of components from a mixture .of hydrocarbons, organic oxygenated compounds, and water, obtained by cataiytically hydrogenating carbon monoxide. cooling the rcsulting vaporous mixture and condensing normally liquid components therefrom, and separating from the cooled mixture a gas phase. a ilrst liquid hydrocarbon phase, and a ilrst aqueous.

phase, all of said phases containing organic olygenated compounds, the improvement which comprises fractionally distilling said first aqueous phase, and separating therefrom an overhead fraction consisting predominantly of low-boiling organic oxygenated compounds substantially free from organic acids, a bottom aqueous fraction containing organic acids substantially free from other organic oxygenated compounds, and an intermediate aqueous fraction containing hydrocarbon-soluble substances and higher-boiling water-soluble organic oxygenated compounds; contacting said rst liquid hydrocarbon phase with said intermediate aqueous fraction; and stratifying and withdrawing therefrom a second liquid hydrocarbon phase containing a diminished proportion of organic oxygenated compounds and a second aqueous phase containing a diminished proportion of hydrocarbon-soluble substances.

2. The process of claim 1 wherein tne fractional distillation of said first aqueous phase is eiected in the presence of a Cs-Cr hydrocarbon mixture, whereby said low-boiling organic oxygenated compounds are withdrawn overhead as an azeotropic mixture with said hydrocarbon mixture.

3. 'Ihe process of claim 1 wherein said gas phase is subsequently contacted with said second aqueous phase containing a diminished proportion of hydrocarbon-soluble substances, whereby organic oxygenated compounds are removed from said gas phase` into said second aqueous phase; and the resulting enriched aqueous phase is recycled to said first aqueous phase.

REFERENCES CITED The following references are of record in the ille oi' this patent:

UNITED STATES PATENTS Number Name Date 2,083,125 Scheuble June 8, 1937 2,216,549 Deanesly Oct. l, 1940 2,259,951 Eversole Oct. 2l, 1941 2,279,052 Michael Apr. 7, 1942 2,299,790 Bludworth Oct. 27. 1942 2,347,682 Gunness May 2, 1944 

1. IN A PROCESS FOR SEPARATELY RECOVERING GENERICALLY DIFFERENT TYPES OF COMPONENTS FROM A MIXTURE OF HYDROCARBONS, ORGANIC OXGENATED COMPOUNDS, AND WATER, OBTAINED BY CATALYTICALLY HYDROGENATING CARBON MONOXIDE, COOLING THE RESULTING VAPOROUS MIXTURE AND CONDENSING NORMALLY LIQUID COMPONENTS THEREFROM, AND SEPARATING FROM THE COOLED MIXTURE A GAS PHASE, A FIRST LIQUID HYDROCARBON PHASE, AND A FIRST AQUEOUS PHASE, ALL OF SAID PHASES CONTAINING ORGANIC OXYGENED COMPOUNDS, THE IMPROVEMENT WHICH COMPRISES FRACTIONALLY DISTILLING SAID FIRST AQUEOUS PHASE, AND SEPARATING THEREFROM AN OVERHEAD FRACTION CONSISTING PREDOMINANTLY OF LOW-BOILING ORGANIC OXGENATED COMPOUNDS SUBSTANTIALLY FREE FROM ORGANIC ACIDS, A BOTTON AQUEOUS FRACTION CONTAINING ORGANIC ACIDS SUBSTANTIALLY FREE FROM OTHER ORGANIC OXGENATED COMPOUNDS, AND AN INTERMEDIATE AQUEOUS FRACTION CONTAINING HYDROCARBON-SOLUBLE SUBSTANCES AND HIGHER-BOILING WATER-SOLUBLE ORGANIC OXGENATED COMPOUNDS; CONTACTING SAID FIRST LIQUID HYDROCARBON PHASE WITH SAID INTERMEDIATE AQUEOUS FRACTION; AND STRATIFYING AND WITHDRAWING THEREFROM A SECOND LIQUID HYDROCARBON PHASE CONTAINING A DIMINISHED PROPORTION OF ORGANIC OXGENATED COMPOUNDS AND A SECOND AQUEOUS PHASE CONTAINING A DIMINSHED PROPORTION OF HYDROCARBON-SOLUBLE SUBSTANCES. 